CN1031578C - Homogeneous olfin polymerization catalyst by abstraction with borane - Google Patents
Homogeneous olfin polymerization catalyst by abstraction with borane Download PDFInfo
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- CN1031578C CN1031578C CN92104968A CN92104968A CN1031578C CN 1031578 C CN1031578 C CN 1031578C CN 92104968 A CN92104968 A CN 92104968A CN 92104968 A CN92104968 A CN 92104968A CN 1031578 C CN1031578 C CN 1031578C
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
Abstract
Addition polymerization catalysts having a limiting charge separated structure corresponding to the formula: LMX<+> XA<->, wherein: L is a derivative of a substituted delocalized PI -bonded group imparting a constrained geometry to the metal active site and containing up to 50 nonhydrogen atoms; M is a metal of Group 4 or the Lanthanide series of the Periodic Table of the Elements; X independently each occurrence is hydride or a hydrocarbyl, silyl or germyl group having up to 20 carbon, silicon or germanium atoms; and A<-> is an anion of a Lewis acid, A, having relative Lewis acidity greater than or equal to that of phenylbis(perfluorophenyl)borane, said anion being compatible with the metal cation, are prepared by contacting a derivative of a Group 4 or Lanthanide metal corresponding to the formula: LMX2, wherein L, M, and X are as previously defined, with the Lewis acid, A.
Description
The present invention relates to a composition material useful as an addition polymerization catalyst. More particularly, the invention relates to a constrained morphology cationic homogeneous catalyst that is removed by use of a lewis acid.
EP-A-416,815 discloses certain constrained morphology metal complexes useful as homogeneous olefin polymerization catalysts. EP-A-418, 044 discloses salts of cationic monocyclopentadienyl metal complexes with Bronsted acids containing non-coordinating compatible anions. EP-A-468,651 discloses an oxidative activation technique for preparing such cationic catalysts.
J.am.chem.Soc.113, 3623-3625 (1991) discloses a method for preparing a "cationic" zirconocene polymeric complex by removing alkyl groups with tris (pentafluorophenyl) borane. Such complexes are said to have activity substantially similar to that of typical Alumoxane (Alumoxane) based complexes. This document does not suggest the applicability of the disclosed process for use on constrained morphology metal catalysts.
J. Orhanomeral. chem.22, 659-663 (1970) discloses the reaction of tetramethyltitanium with triphenylborane. The authors hypothesize that during the reaction an intermediate in the form of cationic titanium is formed which is not isolated. This document does not suggest the suitability of the disclosed reaction for catalytic use.
Previously known methods for preparing cationic metal complexes of limited morphology have the disadvantage that laborious synthetic steps are required to prepare the necessary precursors and the isolated product has a low yield. It would be desirable if an improved technique could be provided for preparing cationic metal complexes of limited morphology while avoiding difficult synthetic steps and low yields.
As has been found, the above-mentioned and other disadvantages of the cationic olefin polymerization catalysts of the prior art can be avoided or at least reduced with the process of the present invention. Surprisingly, the catalyst of the invention is characterized by a high catalytic effect, measured by the polymer yield at a given temperature.
The present invention provides a process for preparing a catalyst having a limited charge separation structure of the general formula:
LMX+XA-in the formula:
l is a derivative of a substituted delocalized π -bonded group conferring a constrained morphology on the metal active site, and containing up to 50 nonhydrogen atoms;
m is a metal of group 4 or lanthanide of the periodic Table of the elements:
x in each case independently is a hydrogen anion or a hydrocarbyl radical containing up to 20 carbon, silicon or germanium atoms, a silyl radical or a germyl radical;
a-is a Lewis acid anion having a relative Lewis acidity greater than or equal to that of phenylbis (perfluorophenyl) borane, which anion is compatible with the metal cation,
the process steps of the method include contacting a group 4 or lanthanide metal derivative of the general formula:
LMX2in the formula
L, M, and X have the same meanings as above.
The molecular formula of the foregoing catalyst composition is called a charge-confined separation structure. However, such catalysts cannot of course be completely charge separated, especially in the solid state. That is, the X group may retain a partial covalent bond with the metal atom M. Thus, such catalysts may also be described as ion pairs having the formula:
LMX..X..A
such catalysts are preferably prepared by contacting the group 4 metal or lanthanide derivative with a lewis acid in an inert diluent such as an organic solvent.
All references herein to the periodic Table of elements are to the periodic Table of elements published and copyrighted by CRC Press, Inc., 1989. In addition, all references to a group or group of numbers refer to the group or group of numbers mapped in thisperiodic table of elements using the IURAC (international union of pure and applied chemistry) system numbering group.
The term "constrained morphology" as used herein means that the metal atom is forced to expose more of the active metal sites as a result of one or more substituents on the substituted delocalized pi-bonded group forming part of a cyclic structure including the metal atom, which, in the cyclic structure,the metal is bonded to both the adjacent covalent moiety and the substituted delocalized pi-bonding group through η5Or other pi-bonding. Of course, the respective linkages between the metal atom and the constituent atoms of the substituted delocalized π -bonded group need not be equivalent. That is, the metal atom may be π -bonded symmetrically or asymmetrically to a substituted delocalized π -bonding group.
The shape of the active metal site is determinedIt is defined as follows: the center of a substituted delocalized pi-bonded group can be defined as the average of the X, Y and Z coordinates, respectively, of the centers of the atoms forming the group. The angle formed by the metal centers between the bonding atom centers of the ligands of the metal complexes with each otherCan be readily calculated by standard methods of single crystal x-ray diffraction. These angles may increase or decrease with the molecular structure of the constrained morphology metal complex. Angle or angles in the complexThe control complex, which is of limited morphology for use in the present invention, differs from a similar control complex in that: the substituents causing the confinement are replaced by hydrogen. One or more angles abovePreferably, the reduction is at least 5%, and more preferably 7.5% as compared to the control complex. More preferably, all key cornersAlso lower than the control complex.
The metal coordination complexes of group 4 metals or lanthanide metals of the present invention preferably have a constrained morphology such that the smallest angles are possiblePreferably<110 °, more preferably<105 °.
Substituted delocalized pi-bonded groups useful in the present invention include any pi-electron containing moiety capable of forming an delocalized bond with a group 4 or lanthanide metal, and may also be substituted with one or more divalent substituents that are also covalently bonded to the metal. Divalent substituents preferably include groups containing up to 30 non-hydrogen atoms, at least one of which is oxygen, sulfur, boron or a member of group 14 of the periodic Table of the elements directly bonded to the delocalized pi-bonded group, and a different atom selected from nitrogen, phosphorus, oxygen and sulfur covalently bonded to the metal. Examples of suitable delocalized pi-bonding groups are cyclopentadienyl or allyl groups, and derivatives thereof.
The term "derivatizing group" as used in the definition L means that each atom of the delocalized π -bonded group can be independently substituted with a group selected from: hydrocarbyl, substituted hydrocarbyl, hydrocarbyl in which one or more hydrogen atoms are replaced by a halogen atom, hydrocarbyl-substituted metalloid radical (wherein the metalloid is selected from group 14 of the periodic Table of the elements) and halo. Suitable hydrocarbyl and substituted hydrocarbyl groups which may be used to form derivatives of delocalized pi-bonded groups contain 1 to 20 carbon atoms and include straight and branched chain alkyl, cycloalkyl, alkyl-substituted cycloalkyl, aryl, and alkyl-substituted aryl groups. In addition, two or more such groups may together form a fused ring system or a hydrogenated fused ring system. Examples of the latter are indenyl, tetrahydroindenyl, fluorenyl, and octahydrofluorenyl. Suitable hydrocarbyl-substituted organometalloid radicals include mono-, di-and tri-substituted organometalloid radicals of group 14 elements, wherein each hydrocarbyl group contains from 1 to 20 carbon atoms. More specifically, suitable hydrocarbyl-substituted organometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylgermyl radicals.
M is preferably a metal of group 4 of the periodic Table of the elements, and most preferably titanium or zirconium. Further, X is preferably C1—C10Most preferred is benzyl, especially methyl.
Very preferred group 4 metal or lanthanide metal derivatives are those corresponding to the formulaMonocyclopentadienyl compounds:in the formula:
m is titanium or zirconium;
cp is a cyclopentadienyl group which is pi-bonded to M and is substituted by at least Z or a derivative thereof;
z is a divalent radical containing oxygen, sulfur, boron, or a member of group 14 of the periodic Table of the elements;
y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y may also together form a condensed ring system;
x has the same meaning as above.
After removal of the X group, the very preferred catalysts of the invention have a limiting potential corresponding to the formulaA load separation structure:
wherein Cp,Z, M, X and A have the same meanings as above.
In the most preferred embodiment, -Z-Y-is an aminosilane or aminoalkanyl radical, preferably containing up to 50 non-hydrogen atoms, most preferably a (tert-butylamino) (dimethylsilyl) or (tert-butylamino) -1-eth-2-yl radical.
The most preferred derivatives of group 4 metals or lanthanide metals are aminosilanediyl-or aminoalkanediyl-compounds of the general formula:in the formula:
m is same as η5-cyclopentadienyl-bonded titanium or zirconium;
r in each case1Independently selected from hydrogen, silyl, alkyl, aryl, and mixtures thereof containing up to 20 carbon or silicon atoms, two or more R on the cyclopentadienyl group1The radicals may optionally form a condensed ring system;
e is silicon or carbon;
x in each case is independently a hydride or an alkyl, aryl or halogen-substituted aryl group containing 20 or fewer carbon atoms;
m is 1 or 2.
Examples of the above-mentioned most preferred metal complex compounds include those wherein R is present on the amino group1Is methyl, ethyl, propyl, butyl, pentyl, hexyl (including branched and cyclic isomers), norbornyl, benzyl or phenyl; cyclopentadienyl is cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl; r on the above-mentioned cyclopentadienyl group1In each case hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl (including branched and cyclic isomers), norbornyl, benzyl, or phenyl; x is methyl, neopentyl, trimethylsilyl, norbornyl, benzyl, methylbenzyl, phenyl, or pentafluorophenyl.
Group 4 metals employable in the practice of theinvention orIllustrative derivatives of the lanthanide metals include [ dimethyl (tert-butylamino) (tetramethyl- η)5-cyclopentadienyl) silane]dibenzylzirconium, [ dimethyl (tert-butylamino) (tetramethyl- η5-cyclopentadienyl) silane dimethyl titanium, [ (tert-butylamino) (tetramethyl- η)5-cyclopentadienyl) -1, 2-ethanediyl]dimethylzirconium [ (tert-butylamino) (tetramethyl- η)5-cyclopentadienyl) -1, 2-ethanediyl-dibenzyltitanium [ (methylamino) (η)5-cyclopentadienyl) -1, 2-ethanediyl]diphenylmethylzirconium [ (methylamino) (tetramethyl- η5Cyclopentadienyls-1, 2-ethanediyl-dineopentyltitans, [ (phenylphosphono) (tetramethyl- η)5-cyclopentadienyl) methylene diphenyltitanium, [ dibenzyl (tert-butylamino) (tetramethyl- η)5-cyclopentadienyl) silane]dibenzylzirconium, [ dimethyl (benzylamino) ((η)5Cyclopentadienyl silane titanium bis (trimethylsilane) [ dimethyl (phenylphosphono) (tetramethyl- η)5-cyclopentadienyl) silane]dibenzylzirconium, [ dimethyl (tert-butylamino) (tetramethyl- η5-cyclopentadienyl) silane dibenzylHafnium-based [ (tetramethyl- η)5-cyclopentadienyl) -1, 2-ethanediyl-dibenzyltitanium [ 2- η]5- (tetramethylcyclopentadienyl) -1-methyl-ethanolate (2) -]-dibenzyltitanium, [ 2- η5- (tetramethylcyclopentadienyl) -1-methyl-ethanolate (2) -) dimethyl titanium, [ 2- η5- (tetramethylcyclopentadienyl) -1-methyl-ethanolate (2) -]-dibenzylzirconium, [ 2- η5- (tetramethylcyclopentadienyl) -1-methyl-ethoxide group (2) -]-dimethylzirconium, [ 2- [ (4a, 4b, 8a, 9, 9 a- η) -9H-fluoren-9-yl]cyclohexanol base (2)]-dimethyltitanium, [ 2- [ (4a4b, 8a, 9, 9 a- η) -9H-fluoren-9-yl]-cyclohexanol base (2)]-dibenzyltitanium, [ 2]-4 a, 4b, 8a, 9, 9 a- η) -9H-9-yl]cyclohexanol base (2)]-dimethylzirconium, and [ 2- [ (4a, 4b, 8a, 9 a- η) -9H-fluoren-9-yl]cyclohexanol base (2)]-dimethylzirconium, and [ 2- [ (4a, 4b, 8a, 9, 9 a- η)]-9H-fluoren-9-yl]cyclohexanol base (2)]-Radical (2) -) dibenzylzirconium.
Other compounds useful in the catalyst composition of the present invention, especially compounds containing another group 4 metal or lanthanide metal. It will of course be apparent to those longer than this row.
Suitable anions are those which either do not coordinate to the metal cation or are only weakly coordinated, thereby leaving sufficient lability to be displaced by a neutral Lewis base. In addition, a "compatible" anion refers to an anion which, when acted as a charge balancing anion in the catalyst system of the present invention, does not transfer anionic substituents or fragments thereof to cations over the desired lifetime thereby forming neutral metallocenes and neutral metal by-products. Such anions do not degrade to neutrality upon decomposition of the initially formed complex and do not interfere with the desired subsequent polymerization or other use of the complex.
Lewis acids having Lewis acidity suitable for use in the present invention may be prepared according to known methods such as those described in J.Am.chem.Soc.1991, 113, 3623-3625, by Marks et al, or Nalurforsohg.1965, 20b, 5-11, by J.Pohlman et al. A preferred method is to use a boron or aluminum halide such as BCl3Or BF3Mixed with the required alkali metal or alkaline earth metal derivatives of one or more substituents. Alternatively, boronic esters such as tris (perfluorophenyl) boronic acid esters may be prepared by reaction of pentafluorophenylphenol with borane-dimethylsulfide complex according to the method of J.org.chem., 43(13), 2731-32 (1978).
The Lewis acidity can be determined empirically or predicted with high reliability by theoretical methods. A preferred method for determining Lewis acidity is to use a crotonaldehyde complex of a Lewis acid at carbon #, a3(H-3) the method discloses a similar method for determining Lewis acidity as reported in R.Childs et al, Can.J.chem., 1982, 802-808, P.Laslo et al, J.Am.chem.Soc.1990, 12, 8750-8754. the unit of determination is △ delta (ppm)The process can be carried out at 25 ℃ or less without harmful effects.
The difference in chemical shift between the 3-hydrogen of the uncomplexed crotonaldehyde and the 3-hydrogen of the complexed Lewis acid adduct is determined, this difference in chemical shift (delta, in ppm) is related to the Lewis acidity of the substance under investigation, the trend being that the greater the 3-hydrogen moves towards the lower magnetic field, the greater the Lewis acidity of the compound detected, the greater the chemical shift difference of phenylbis (perfluorophenyl) borane of 0.77ppm, the greater the Lewis acidity of the compound, the chemical shift difference △ delta greater than 0.77, the preferred Lewis acid acidity is between 0.77 and 1.49, and more preferably between 1.0 and 1.49, therefore, with the aid of Childs et al, the Lewis acid suitable for the present invention is the relative acidity [ compared to phenylbis (perfluorophenyl) borane], △ delta- △ delta ≧ 0, the acid [ △ delta]is the Lewis acidity of the Lewis acid of the selection Lewis acid, △ delta ° is the Lewis acid of phenylbis the phenylbis (perfluorophenyl) borane, the preferred is between 0.72 and 0.72.
The disadvantageous activity of Lewis acids comprises the use of the cationic part of the catalyst, LMX+One or several groups are removed from the anion. Groups that are easily removed include halides attached directly to the central group 13 metalloid. Thus, the most preferred inactive lewis acids are lewis acids without a directly concentric group 13 metalloid, especially boron-linked halogen group. Unless otherwise indicated, the most preferred Lewis acids are boron compounds having no halogen moiety directly attached to the boron.
Theoretical methods can also be used to calculate the acidity of the lewis acids suitable for use in the present invention. Several commercially available computer programs can be used to calculate the acidity of the lewis acid. According to a preferred method, the proposed reaction of the Lewis acid with the Lewis base to form a complex can be used to calculate the total energy of the theoretical structure of the selector molecule. The calculated molecule with the larger heat of complexation indicates that its Lewis acidity is also larger. A program such as GAUSSIAN90, or similar molecular modeling software, can be used to model and analyze such materials.
First, the optimum parameters for the initial structure are selected by minimizing the calculated total energy for all degrees of freedom, bond length, bond angle, and twist angle, then the heat of reaction is calculated as the difference between the total energy of the product and the total energy of the reactants (△ H), e.g.
Σ E (product) — Σ E (reactant) where E is approximately equal to the quantum mechanical energy (E) of the reactant and product at absolute zero (0 °, kelvin)QM)。
By the above method, a compound can be calculated for a Lewis base (e.g., CH) using the following formula3Anions or ammonia):
According to the empirical and theoretical methods described above, very preferred Lewis acids are tris (pentafluorophenyl) borane, tris (2, 3, 5, 6-tetrafluorophenyl) borane, tris (2, 3, 4, 5-tetrafluorophenyl) borane, tris (3, 4, 5-trifluorophenyl) borane, tris (1, 2, 2-trifluoroethylene) borane, phenylbis (perfluorophenyl) borane, tris (3, 4, 5-trifluorophenyl) aluminum, tris (perfluorophenyl) borate, 1, 3, 5-cyclohexanetriol borate (cyclohexaner-1, C-3C-5-triol borate), and 1, 1, 1-trimethylolethane borate (2, 6, 7-trioxa-1-bora-4-methylbicyclo [ 2.2.2]octane) (the latter two compounds can be prepared by the method of U.S. Pat. No. A-2,909,560, by 1, 35-cyclohexanetriol or 1, 11-trimethylolethane and boric acid).
Without wishing to be bound by any particular theory of operation, it is believed that this lewis acid causes the removal of the X group and becomes an anionic form in the process. The Lewis acid is a cation obtained in comparison with LMX+In the case of stronger Lewis acids, the results are considered to beHas practical significance for the invention. This particular Lewis acid of the present invention is very effective in this regard.
In general, the catalyst of the invention can be obtained by mixing the two components (the group 4 metal or lanthanide derivative and the Lewis acid) in a suitable solvent at a temperature of from-100 ℃ to 300 ℃, preferably from 25 ℃ to 50 ℃. Suitable solvents include straight and branched chain hydrocarbons such as isobutane, butane, pentahexane, heptane, octane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane; perfluorinated hydrocarbons such as perfluorinated C4—10An alkane; and aromatic compounds and alkyl-substituted aromatic compounds such as benzene, toluene and xylene. Suitable solvents also include liquid olefins that may be used as monomers or comonomers including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1, 4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene, and vinyltoluene (including all the individual iso-olefins)A structure or a mixture thereof). Preferred solvents are aliphatic hydrocarbons, especially C5—C10Alkanes or cycloalkanes and mixtures thereof.
The catalyst can be used for polymerizing addition polymerizable monomers containing 2 to 1000 carbon atoms. Examples include: ethylenically unsaturated monomers, acetylenic compounds, conjugated or non-conjugated dienes, polyenes, and carbon monoxide. Preferred addition polymerizable monomers are olefins or diolefins having 2 to 18 carbon atoms. Preferred monomers include C2-18α -alkenes, especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene other preferred monomers include styrene, halogen or alkyl substituted styrene, tetrafluoroethylene, vinylbenzocyclobutane, 1, 4-hexadiene, norbornene, and substituted norbornenes such as 5-ethylidene-2-norbornene, the most preferred monomer is α -alkene containing 2-12 carbon atoms, which may beThe catalyst may also be used to polymerize α -olefin, diolefin, and/or hydrocarbon unsaturated monomer in combination with other unsaturated monomer.
In general, the polymerization can be carried out under the conditions known from the Ziegler-Natta type or Kaminsky-Sinn type polymerization reactions of the prior art, i.e.at temperatures of from 0 to 250 ℃ and pressures of from atmospheric to 1000 atmospheres (100 MPa). Suspension polymerization, solution polymerization, slurry polymerization or other polymerization methods may be employed if desired. The catalyst may be used on a support of some kind, but is preferably used in a homogeneous manner. Of course, it is contemplated that if the components of the catalyst are added directly to thepolymerization process. And the catalyst system can be generated in situ using a suitable solvent or diluent (including condensed monomer) in the process. However, it is preferred that the catalyst is added to the polymerization mixture after it has been prepared in a separate step in a suitable solvent.
It is believed that this active catalyst form of the invention will have metal centers that remain cationically unsaturated and contain metal-carbon bonds active with respect to olefins, diolefins and acetylenically unsaturated compounds. Additionally associated with this metal center is a charge-balancing anionic residue of the formula XA-. As noted above, the catalyst can also be present in less than a fully charge separated configuration.
The catalyst formed by the process of the present invention may be retained in solution or separated from the solvent, isolated, and stored for subsequent use. As noted above, the catalyst may also be prepared by placing the various components into a polymerization vessel to be contacted and reacted, thereby producing the catalyst in situ during the polymerization reaction.
The equivalent ratio of the derivative of the group 4 metal or lanthanide metal compound to the Lewis acid used is preferably 0.1: 1 to 10: 51 (complex: Lewis acid), more preferably 0.2: 1 to 5: 1, still more preferably 0.5: 1.0 to 1: 2. In most polymerizations, a catalyst is employed which is a polymerizable compound in an equivalent ratio of 10-12∶1~10-11 to 10-9∶1~10-4Preferably 1.
The catalyst of the invention, especially one based on titanium, is advantageously characterized in that when it is used to copolymerize olefins (either alone or in admixture with dienes), the amount of higher molecular weight olefin or diene incorporated into the copolymer is significantly increased as compared to copolymersmade with more conventional Ziegler-Natta type catalysts. In addition, the catalyst of the present invention has a higher activity when compared to the aluminoxane containing constrained morphology catalyst. The catalytic efficiency (measured as weight of polymer produced/weight of catalyst) of the catalysts of the invention is generally at least five times greater than that of a similar catalyst using an aluminoxane.
The catalyst can generally be selected so that the resulting polymer will be relatively free of significant amounts of certain minor impurities such as aluminum, magnesium, and chlorides commonly found in polymers made using Ziegler-Natta type catalysts. The polymer products obtained with the catalysts of the invention have a broader range of applications than polymers obtained with more conventional Ziegler-Natta type catalysts, which latter catalysts comprise an alkyl metal halide such as magnesium chloride or an alkyl aluminium chloride.
While the present invention has been described, the following examples are provided for the purpose of further illustration and are not to be construed as limiting. All parts and percentages are by weight unless otherwise indicated. General polymerization procedure
Ethylene, propylene and hydrogen were purified by passage through columns containing 13X molecular sieves, activated alumina, and a minor amount of oxygen removal catalyst (the copper/manganese catalyst loaded alumina is available from Englhardt corporation under the designation Q-5). The solvent and octene were degassed with nitrogen and then purified by passage through columns containing 13X molecular sieves, activated alumina, and a trace of oxygen removal catalyst. Styrene, which did not contain phenylacetylene, was degassed with nitrogen and then purified by passage through an activated alumina column. A2-liter stirred autoclave was charged with the required amounts of certain solvents and comonomers.
Expanded by differential pressure from a 75 ml feed vesselHydrogen was added to the reactor. The pressure difference of hydrogen being that of the hydrogen feed tank after the hydrogen has been fed to the 2 liter reactor containing solvent and comonomerThe pressure difference between the initial pressure and the final pressure. The reactor was heated to the polymerization temperature and saturated with ethylene to the desired pressure. In a dry box, the desired amount of 0.0050M metal complex solution (solvent mixed alkanes, available from Exxon chemical company under the trademark Isopar E) was injected by syringeTMThe solvent can also be toluene) is injected into the catalyst solution (Isopar solvent)_E or toluene), the metal complex is mixed with a lewis acid co-catalyst. More solvent may also be added to facilitate transfer of the catalyst solution to the reactor. The solution was then transferred to a catalyst addition tank and injected into the reactor.
The polymerization was allowed to proceed for the desired time, the solution was drained from the bottom of the reactor and the polymerization was stopped with isopropanol. Adding hindered phenol antioxidant (Irganox)_1010 from Ciba-Geigy), the polymer was dried overnight. Residual solvent was removed in a vacuum oven overnight.
Adopts a micro-melting index instrument (CS-127 MF type, manufactured by Custom scientific instruments Co., Ltd.) according to ASTMD-1238, step A, Condition E, determining the melt index of the polymer. The density was determined by buoyancy of the molded sample in butanone. Experimental determination of Lewis acidity
Lewis acidity of phenylbis (perfluorophenyl) borane is determined by nuclear magnetic resonance essentially as described in R.Childs et al, Can.J.Ghem, 1982, 60, 802-808. All manipulations were carried out using standard Schlenkand/or high Vacuum methods, or in an inert glove box (Vacum atmosphers) under protection of circulating dry ammonia, the oxygen content of which was constantly monitored with an oxygen analyzer and maintained at<1 ppm. Crotonaldehyde used is derived from calcium hydrideRefining by vacuum transfer, dichloromethane-d2(CD2Cl2) By means of slave P2O5Vacuum transferring for refining.
Proton nuclear magnetic resonance spectra were recorded by a Varian VXR-300 or Varian Gemini 300 nuclear magnetic resonance spectrometer. By CD2Cl2Residual CHDCl in2(1H, δ 5.32) were determined relative to tetramethylsilane. The preparation method of the nuclear magnetic resonance sample comprises the following steps: CD with crotonaldehyde added with a suitable amount of a Lewis acid compound2Cl2The solution (-20 ℃) and the sample was allowed to warm slowly to room temperature. The resulting solution was stoichiometric with a 50% excess of lewis acid reagent, with a total concentration of reactants of about 0.3M. Then record1H nuclear magnetic resonance spectrum, and measuring the Lewis acid adduct of the butenal and H-3 nuclear magnetic resonance shift of the free butenal. Theoretical calculation of Lewis acidity
The structure and energy are calculated using one or several of the following standard methods of theory of electronic structures.
1. AM1 — Dewar semi-empirical method according to the approximate molecular orbital theory. AM1 has been parametrized to fit the experimental data chosen. The calculation of AM1 is well known to those who have grown in this area and is described in, for example, m.j.s.dewar, e.g.zoebisch, e.f.healy and j.j.p.stewart, j.am.chem.soc., 1073902 (1985); m.j.s.dewar and eveg.zoebisch, j.mol. Struct, (THEOCHEM), 180, 1 (1988):m.j.s.dewar, c.jie, and e.g.zoebisch, Organometallics, 7, 513 (1988); m.j.s.dewar and c.jie, Organometallics, 6, 1486 (1987); m.j.s.dewar and k.m.merz, jr., Organome-tallics, 7, 522-4 (1988); m.j.s.dewar and c.jie, Organometallics, 8, 1547 (1989); m.j.s.dewar and c.jie, Organometallics, 8, 1544-7 (1989) and m.j.s.dewar and a.j.holder, Organometallics, 9, 508 (1990).
AM1 calculations were performed using the Program MOPAC, version 5.00, available from Quantum Chemistry Program Exchange (QCPE), Department of Chemistry, Indiana Uni-Versize, Bloomington, Indiana 47405. The procedure is further described in the MOPAC manual (j.j.p.stewart, frankj. Seiler, res.lab., u.s.air ForceAcademy, colo.spgs., co.80840).
2. HF (restricted harttree-focus) is a strict (from the beginning, without adjustable parameters) method. Result of HF employingGAUSSIAN_90 programs and the well-known 3-21 g algorithm system. The 3-21 g algorithm is a valence double Zeta (ζ) algorithm. The output of the Gaussian90 is obtained by the method,revision j. was purchased from Gaussian (Rjttsburgh PA, 1990).
3-21G algorithm systems are well known in the art and are described in documents such as w.J.Hehre, L.Radiom, P.V.R.Schleiyer, and J.A.Pople, Ab initio molecular Orbital Theory, Wiley, New York (1986); pietro, w.j., et al, j.am.chem.soc.104, 5039-48 (1982); M.S. Gordon et al, J.Am.chem.Soc.104, 2797-803 (1982); J.S. Binkley et al, J.am.ChemSoc, 102, 939-47 (1980); K.D.Dobbsand W.J.Hehre, J.Compout.chem.8, 880-93 (1987); k.d. dobbs and w.j.hehre, j.comput.chem.8, 861 (1987); k.d.dobbs and w.j.hehre, j.comput.chem.9, 801 (1988); k.d.dobbs and w.j.hehre, j.comput.chem.7, 359 (1986).
Example 1
1 ml of a 0.005M solution of tris (pentafluorophenyl) borane in toluene was combined with 1 ml of 0.005M [ (tert-butylamino) dimethyl (tetramethyl- η)5-cyclopentadienyl) silane dibenzyltitanium [ (C)5Me4)SiMe2—N(t—Bu)〕Tibz2Toluene solution to prepare a catalyst solution,the latter compound is obtained by (tert-butylamino) dimethyl (tetramethyl- η)5The dichlorides are obtained by reacting 1, 2, 3, 4-tetramethylcyclopentadienyl lithium with (N-tert-butylamino) (dimethyl) chlorosilane, then converting it into the dilithium salt, and reacting it with TiCl to form (N-tert-butylamino) dimethyl (tetramethyl- η) with a closed ring structure5Cyclopentadienyl) titanium chloride and oxidation of the metal centre with dichloromethane to give (N-tert-butylamino) dimethyl (tetramethyl- η)5Cyclopentadienyl) titanium dichloride. The mixture of the two components was shaken at 25 ℃ for 10 seconds and the resulting catalyst solution was significantly darker than the original orange-red titanium-containing solution. Polymerisation
In 2The catalyst solution was transferred in a liter reactor from 1 liter of Isopar ETM0.2 liter of 1-octene was mixed with a mixture of ethylene (31 atm, 3.1 MPa). The reactants were degassed and refined beforehand, and the reactor contents were heated to 130 ℃. The reactor temperature immediately rose by 7 ℃.
Ethylene was supplied at a pressure of 3.1 mpa. After ten minutes, the contents of the reactor were taken out and devolatilized, thereby obtaining 80.0 g of an ethylene-octene copolymer having a micro-melt index of 0.104.
Example 2
1 ml of a 0.005M solution of tris (pentafluorophenyl) borane in toluene was combined with 1 ml of a 0.005M solution of (tert-butylamino) dimethyl (tetramethyl- η)5-cyclopentadienyl) silanedibenzylzirconium [ (C)5Me4)SiMe2—N(t—Bu)Zrb2Toluene solution to prepare a catalyst solution,the latter compound was prepared in the same manner as in example 1. The mixture was shaken at 25 ℃ for 10 seconds and the resulting catalyst solution was slightly darker than the original bright yellow zirconium-containing solution. Polymerisation
The catalyst solution (10. mu. mol in 2 ml Isopar) was placed in a 2 l reactorTME in) 0.8 liter IsoparTME, 0.4 liter of propylene. The contents of the reactor were heated to 50 ℃. After 45 minutes, the contents of the reactor were taken out and devolatilized, whereby 30.1 g of polypropylene having a micro melt index of 24.3 and a syndiotactic index (measured in terms of racemic triads) of 83.5 was obtained.
Examples 3 to 37
The metal complex of examples 3-37 was (tert-butylamino) dimethyl (tetramethyl-5-cyclopentadienyl) silanetitanium, [ (C)5Me4)SiMe2N(t—Bu)〕TiMe2The Lewis acid is tris (perfluorophenyl) borane, B (C)6F5)3. The polymerization time was 10 seconds for all examples. The results of examples 3 to 37 are shown in Table 1.
TABLE 1
Temperature Hydrogen Difference ethylene 1-octene Lewis acid titanium melting refers to density example (. degree. C.) pressure, kilopascal megapascal (ml) (micromole) yield, gram number (I2) (g/ml) 32043003.4501510.0015.137.9-41903403.45096.0018.727.54-519003.45096.006.30.04-61901703.45096.0025.85.5-71763003.45064.0030.210.6-82101703.4501510.008.621.23-91901703.45096.00145.23-10204503.4501510.007.11.6-111701703.45064.0040.61.99-121901703.45096.0017.13.54-131901703.45096.0016.75.34-14176503.45064.0026.20.2-151901703.45096.0020.44.34-1617003.45064.00280.04-1721003.4501510.001.1-181633403.28551.251.2522.43.540.9220191631703.28551.251.2545.51.040.9173201501703.28551.251.2577.31.350.9115
TABLE 1(continuous) examples temperature Hydrogen Difference ethylene 1-octene Lewis acid titanium melt index Density
Pressure (. degree.C.), kilopascal (milliliter) (micromole) yield, grams (I2) (g/ml) 211631703.28551.251.2549.11.070.9189221702803.28281.251.2530.11.930.9310231631703.281001.251.2543.25.60.9077241631703.28551.251.2510.20.760.907925155693.28281.251.2535.50.070.9190261631703.28551.251.2539.71.440.917327170693.28821.251.2523.72.040.912528170 "3.28281.251.2522.90.190.9223291552803.28821.251.25444.240.9116301631703.28101.251.2516.10.150.93373116303.28551.251.2510.20.580.9154321631703.28551.251.2530.81.140.9192331702803.28821.251.2522.69.950.920634155693.28821.251.25421.010.9096351751703.28551.251.2517.73.780.9214361631703.28551.251.2532.10.810.9176371552803.28281.251.2531.30.360.9266
Examples 38 to 57
The catalysts and procedures of examples 3-37 were used except that 1000 ml of Isopar was added to the reactor_E, then adding different amounts of propylene. The desired amount of hydrogen is then added and the solution is heated to the reaction temperature. The solution was then saturated with ethylene at 475Psig (pounds per square inch gauge), i.e., 3.38 mpa. Complexing equimolar amounts of metal[ (C) is5Me4)SiMe2N(t—Bu)〕TiMe2With Lewis acid, B (C)6F5)3In 2 ml Isopar_E and transferring the solution into a reactor to start the polymerization. The reaction was allowed to proceed for 15 minutes while ethylene was supplied at a pressure of 475Psig (3.38 mpa) as required. The propylene content of the polymers is determined by means of carbon nuclear magnetic resonance spectroscopy, using the methods described in J.C.Randall, Rev.Macromo.chem.Phys.29 (2)&3) 201-317, (1989). The results are shown in Table II.
TABLE 2
Propylene temperature titanium hydride melting refers to propylene density example (g) (. degree. C.) differential pressure, kilopascals (micromoles) yield, grams(I2)(mol%) (g/ml) 3810095690.50070.93.55130.70.85203986550550.375109.00.67140.00.85134013086140.32598.10.18441.20.852241100950.32571.70.06331.90.851642130104550.75099.56.98450.20.85144310095340.37592.80.95646.00.85184410095340.37588.70.77738.00.8516455095340.37579.10.37224.20.8631467086 550 .375 94.7 1.098 30.0 0.8544 47 100 80 340 .300 96.8 0.261 34.3 0.8518 48 70 104 550 .500 75.6 2.122 30.0 0.8540 49 100 110 340 .750 91.6 4.093 38.2 0.8536 50 100 95 340 .500 96.5 1.203 38.1 0.8501 51 70 86 140 .250 72.8 0.000 28.2 0.8559 52 100 95 340 .325 79.2 0.796 35.8 0.8491 53 100 95 340 .325 82.3 0.674 37.5 0.8518 54 70 104 140 .750 92.6 0.830 32.9 0.8533 55 100 95 340 .325 82.5 0.733 35.2 0.8517 56 130 104 140 .500 84.1 1.697 43.2 0.8497 57 100 95 340 .325 83.1 0.503 36.8 0.8508
Examples 59 to 77
The procedure of examples 3 to 37 was followed except that different amounts of styrene and then Isopar were charged into the reactor_E make the total volume of liquid 1000 ml. Different amounts of propylene were added. The solution was heated to the reaction temperature. The solution was then saturated with ethylene according to a pressure of 480Psig (3.41 mpa). Equimolar amounts of the metal complex [ (C)5Me4)SiMe2N(t—Bu)〕TiMe2With Lewis acid B (C)6H5)3In 2 ml Isopar_E and transferring the solution into the reactor to start polymerization. The reaction was allowed to proceed for 10 minutes while ethylene was supplied at a pressure of 480Psig (3.41 mpa) as required. The results are shown in Table III. If desired, the propylene and styrene contents can be determined by means of carbon 13 nuclear magnetic resonance spectroscopy.
TABLE 3
Temperature of propylene styrene titanium melt refers to the yield in grams (deg.C) (micromoles) of example (g) (mL), grams (I2) 5870121821.2557.30.07859100225101.2534.30.81960703291183.7531.47.494611301211182.5040.637.20062*100 400 100 3.75 51.2 2.557 63 130 329 118 3.75 38.2 29.000 64 100 225 100 1.25 40.6 0.893 65 130 329 82 1.25 73.4 0.214 66 100 50 100 1.25 71.2 2.607 67 70 121 118 2.50 42.2 7.415 68 150 225 100 1.50 53.7 2.784 69 100 225 100 1.25 40.2 0.996 70 100 225 100 1.25 46.6 0.982 71 50 225 100 1.50 44.8 0.566 72 100 225 130 3.75 27.3 99.100 73 100 225 100 1.25 51.6 1.221 74 100 225 100 1.25 45.1 0.920 75 70 329 82 1.25 53.8 0.125 76 100 225 70 0.75 64.9 0.048 77 130 121 82 0.75 79.1 0.210*30 mol% of propylene and 4.4 mol% of styrene
Examples 78 to 100
The procedure of examples 3 to 37 was followed except that different amounts of styrene andthen Isopar were charged into the reactorE, making the total volume of the liquid to be 1000 ml. Different amounts of hydrogen were added. The solution was heated to the reaction temperature. The solution was then saturated with ethylene according to a pressure of 475Psig (3.38 mpa). Equimolar amounts of the metal complex [ (C)5Me4)SiMe2N(t—Bu)〕TiMe2With Lewis acid, B (C)6F5)3In 2 ml Isopar_And transferring the solution into a reactor to start polymerization. Adding the two additional portions of the complex and the Lewis acid into the reactor at an interval of 5-10 minutes. The total amount of catalyst added (calculated on titanium basis) is shown in Table IV. After the final addition of catalyst was complete, the reaction was allowed to proceed for 10 minutes, with ethylene being supplied at a pressure of 475Psig (3.38 mpa) as soon as required throughout the polymerization. The results are shown in Table IV.
TABLE 4
Styrene temperature Hydrogen catalyst melt index styrene content example (ml) (. degree. C.) (kilopascal) (micromolar) yield, grams (I2) (mol%) 7812514505.024.00.2090.87975145765.044.80.4360.580225145767.537.52.1171.5812341361107.559.81.8841.782175145697.552.51.4711.383175145 "7.552.01.3521.484234154287.534.42.4471.5851161361105.865.10.739-86275145697.546.22.0551.987175160" 7.531.17.1111.288175130 "3.046.30.335-89116154" 7.549.24.0611.090234154 "7.539.89.4171.6911751451407.555.13.494-92175145697.553.11.144-93116154287.546.40.7100.894175145697.552.61.1341.495234136285.045.50.270-96175145697.552.21.185-9717514507.550.20.465-98175145697.551.31.126-9975145" 7.563.00.4890.6100116136285.052.50.115-
Example 101
The polymerization procedure according to examples3-37 was followed in 2 ml Isopar_E was mixed with 1.25. mu. mol of (tert-butylamino) dimethyl (tetramethyl- η)5-cyclopentadienyl) silane dibenzyltitanium [ (C)5Me4)SiMe2N(t—Bu)〕TiBz2And 1.25 micromoles of a Lewis acid, B (C)6F5)3. The reaction temperature was 160 ℃.10 g of propylene and hydrogen were added at a differential pressure of 100Psi (0.7 MPa). The ethylene pressure was 460Psig (3.3 MPa). The polymerization time was 5 minutes. 22.9 g of an ethylene/propylene copolymer were isolated.
Example 102
The polymerization procedure of example 101 was followed at 2 ml Isopar_E was mixed with 1.00. mu. mol of [ (C)5Me4SiMe2N(t—Bu)〕TiMe2And 1.00 micromole of a Lewis acid B (C)6F5)3. The reaction temperature was 90 ℃. 1000 ml of Isopar were added to the reactor_E and 200 ml of 1-octene, without addition of hydrogen. The ethylene pressure was 500Psig (3.55 MPa). The polymerization time was 15 minutes, 85.9 g of an ethylene/octene copolymer having a density of about 0.87 g/ml and a melt index (I)2) Is 0.3.
Example 103
Preparation of tetrahydrofluorene by polymerization of (tert-butylamino) dimethyl (tetrahydrofluorene) silanetitanium dimethyl derivative
15 g (90.2 mmol) of fluorene are dissolved in 200 ml of tetrahydrofuran(THF)/ethylenediamine (ratio 1: 1) solution. The solution was cooled with an ice bath while stirring. 3.13 g of lithium (451.2 mmol) were added in small portions. After all the lithium has been added, the solution is stirred for 2 hours, whereupon the dissolution of lithium takes place. The resulting solution was then poured into a mixture of HCl/ice. The solution was extracted with ether. The organic washes were combined, washed with water, and MgSO4And (5) drying. The solution was filtered and the solvent removed using a rotary evaporator. The crude product was purified by dissolving in hexane and passing through a silica gel column to give, after removal of the solvent, 11.4 g (75% yield) of the product. Preparation of lithium tetrahydrofluorenylate
10 feet of tetrahydrofluorene (59 mmol) were dissolved in 75 ml of pentane. To the solution was added 21 ml of n-butyllithium (2.65 mol) dropwise over a period of 20 minutes, and the solution was stirred overnight whereupon a white solid precipitated. The solid was collected by filtration, washed with pentane and dried under reduced pressure to give 7.14 g (70% yield) of the product. Preparation of (N-tert-butylamino) (dimethyl) (tetrahydrofluorenyl) silane
To 100 ml of THF was added 5.78 g (34.9 mmol) of Clsime2NHCMe3(prepared as described in J.Prake.chem, 24 (3-4), 226-30 (1964)). To the solution was added 6.15 g (34.9 mmol) of lithium tetrahydrofluorenylate. The solution was refluxed for 10 minutes and cooled to room temperature. Gas chromatography analysis indicated that the reaction was complete. The solvent was removed under reduced pressure, the residue was extracted with pentane, filtered and the solvent was removed under reduced pressure, whereby 9.80 g of the product was obtained (yield 94%).
Preparation of (N-tert-butylamino) (dimethyl) (tetrahydrofluorenyl) silane dilithium.
9.80 g (32.8 mmol) (N-tert-butylamino) (dimethyl ether)Phenyl) - (tetrahydrofluorenyl) silane was dissolved in 100 ml of diethyl ether. To this solution was added 26.6 ml (70.6 mmol) of n-butyllithium (2.65M) dropwise. After the addition was complete the solution was stirred for 2 hours and the solvent was subsequently removed under reduced pressure to give an orange oily residue which solidified by trituration with pentane to give 11.86 g (98% yield) of a yellow solid which was identified by NMR spectroscopy as being (N-tert-butylamino) (dimethyl-amino)) Diethyl ether adduct of (tetrahydrofluorenyl) silane dilithium (3/4 Et per molecule)2O [ (N-tert-butylamino) (dimethyl) (tetrahydrofluorenyl) silane]titanium dichloride ([ (tetrahydrofluorenyl) SiMe)2N(t—Bu)〕TiCl2Preparation of
6 g (16.1 mmol) of TiCl are introduced3(THF)3Dissolved in 75 ml of THF. To this solution was added 5.92 g (16.1 mmol) of solid (N-tert-butylamino) (dimethyl) (tetrahydrofluorenyl) silane dilithium (3/4 diethyl ether) with stirring. The solution was then stirred for 45 minutes, after which time PbCl was added2(2.25 g, 8.1 mmol) and the solution is stirred for an additional 45 minutes. THF was removed under reduced pressure. The residue was extracted with toluene, the solution was filtered, and the toluene was removed under reduced pressure. The residue was triturated with pentane and the solution was cooled to-20 ℃ for 3 hours. The red precipitate was collected by filtration, washed with cold pentane and dried in vacuo to afford 5.00 g of product (75% yield). [ (N-tert-butylamino) [ dimethyl) (tetrahydrofluorenyl) silane]dimethyl titanium ([ (tetra-hydro) SiMe)2N(t—Bu)〕Ti(CH3)2Preparation of
5.0 g of [ (N-tert-butylamino) (dimethyl) (tetrahydrofluorenyl) silane]titanium dichloride (12 mmol) were suspended in 100 ml of diethyl ether. To this suspension was added dropwise, with stirring, 8.40 ml of methylmagnesium iodide (MeMgI in ether, 3.0M), after the addition was complete, the solution was stirred for 40 minutes, after which the ether was removed under reduced pressure, the residue was extracted with pentane, the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to give 3.48 g of the product (77% yield) which was polymerized
Following the procedure of example 102, in 2 ml Isopar_E was mixed with 2.00. mu. mol of [ (tetrahydrofluorenyl) SiMe2N(t—Bu)〕TiMe2And 2.0 micromoles of a Lewis acid, B (C)6F5)3. The reaction temperature was 130 ℃.808 g of Isopar were charged to the reactor_E and 100 g of 1-octene. No hydrogen was added. The ethylene pressure was 500Psig (3.55 MPa). The polymerization time was 15 minutes. 41.1 g of an ethylene/octene copolymer was isolated.
Example 104
Following the procedure of example 103, exceptCharacterized in that the amount of Isopar is 2 ml_E was mixed with 2.50. mu. mol of [ (tetrahydrofluorenyl) SiMe2NN(t—Bu)〕TiMe2And 2.50 micromoles of Lewis acid B (C)6F5)3To form a catalyst. The reaction temperature was 150 ℃. 829 grams of Isopar_E and 29 g of 1-octene were added to the reactor without hydrogen. The ethylene pressure was 500Psig (3.55 MPa). The polymerization time was 15 minutes, and 11.4 g of an ethylene/octene copolymer was isolated.
EXAMPLE 105 preparation of 4, 5, 6, 7-tetrahydro-1-methylinden-3-one by polymerization of (tert-butylamino) dimethyl (1, 3-dimethyl-5, 6, 7, 8-tetrahydroindenyl) silanetitanium dimethyl derivative
Cyclohexene (27.3 g, 0.33 mol), crotonic acid (28.7 g, 0.33 mol) and polyphosphoric acid (300 ml) were mechanically stirred under nitrogen at 60 ℃ for 30 minutes. The slurry was poured into water and the aqueous solution was extracted with ether. Sequentially with 10% NaHCO3The ether extracts were washed with saturated NaCl solution. Then using anhydrous MgSO4The organic extract is dried. Filtering the solution, and removing the solvent under reduced pressure. The crude product was distilled under vacuum (bp 87-92 ℃, pressure 5 torr, 0.7 kpa) to yield 32.6 g (66% yield) of the purified material. Preparation of 7, 9-dimethylbicyclo- [ 4.3.0]-nonan-1 (6), 7-diene
Methyllithium (1.5M, 96 ml) was added dropwise to a solution of 4, 5, 6, 7-tetrahydro-1-methyl-inden-3-one (17.7 g, 0.118 mol) in 50 ml of diethyl ether under argon, and the reaction mixture was refluxed for 18 hours. After this time the mixture was hydrolyzed and the reaction mixture was extracted with ether. With anhydrous MgSO4The ether extracts were dried and filtered. 0.5 ml of 6M HCl was added to the ether solution and the solution was stirred for one hour. Thereafter, the ether solution was washed with water and then with anhydrous MgSO4Drying, filtering and concentrating. Distillation under reduced pressure gave 8.0 g (45% yield) of product. Preparation of lithium 1, 3-dimethyl-5, 6, 7, 8-tetrahydroindene
To 100 ml of pentane was added 7, 9-dimethylbicyclo- [ 4.3.0]-nonane-1 (6), 7-diene (5.0 g, 33.5 mmol). To this solution was added dropwise a solution of n-butyllithium in pentane (2.7M, 13 ml), and the mixture was stirred for 12 hours. The resulting white precipitate was collected by filtration, washed with pentane and dried under reduced pressure to give 5.02 g (97% yield) of the product. Preparation of (N-tert-butylamino) (dimethyl) (1, 3-dimethyl-5, 6, 7, 8-tetrahydroindenyl) silane
0.77 g ClSiMe was added to 50 ml THF2NHCMe3(4.67 mmol). To this solution was added 0.75 g (4.67 mmol) of lithium 1, 3-dimethyl-5, 6, 7, 8-tetrahydroindene. The solution was refluxed for 10 minutes and it was cooled to room temperature again. Gas chromatography analysis indicated that the reaction was complete. The solvent was then removed under reduced pressure, and the residue was extracted with pentane, filtered, and the solvent was removed underreduced pressure, whereby 1.21 g of the product was obtained (yield 94%). Preparation of (N-tert-butylamino) (dimethyl) (1, 3-dimethyl-5, 6, 7, 8-tetrahydroindenyl) silane dilithium
1.21 g (4.36 mmol) of (N-tert-butylamino) (dimethyl) (1, 3-dimethyl-5, 6, 7, 8-tetrahydroindenyl) silane were dissolved in 100 ml of diethyl ether. To this solution 5.72 ml (9.17 mmol) of n-butyllithium (1.6M in pentane) were added dropwise. After the completion of the addition, the solution was stirred for 2 hours, followed by removal of the solvent under reduced pressure, whereby a yellow oily residue was obtained which was solidified by trituration with pentane to obtain 1.00 g (yield 79%) of a product as a tan solid.[ (N-tert-butylamino) (dimethyl) (1, 3-dimethyl-5, 6, 78-tetrahydroindenyl) silane]titanium dichloride ([ (1, 3-dimethyl) -tetrahydroindenyl) SiMe2N(t—Bu)〕TiCl2) Preparation of
0.64 g (1.72 mmol) of TiCl are dissolved in 75 ml of THF3(THF)2. To this solution was added 0.50 g (1.72 mmol) of (N-tert-butylamino) (dimethyl) (1, 3-dimethyl-5, 6, 7, 8-tetrahydroindenyl) silanedilithium as a solid with stirring. The solution was then stirred for 45 minutes, after which time PbCl was added2(0.239 g, 0.86 mmol) and the solution was stirred for 45 minutes. THF was removed under reduced pressure. The residue is extracted with toluene, the solution is filtered and removed under reduced pressureToluene. The residue was then triturated with pentane and the solution was cooled to-20 ℃ for 3 hours. The product was collected by filtration, washed with cold pentane and dried in vacuo, whereby 0.32 g (47% yield) of the product was obtained. [ (N-tert-butylamino) (dimethyl) (1, 3-dimethyl-5, 6, 7-8-tetrahydroindenyl) silane]dimethyltitanium ([ 1, 3-dimethyl-tetrahydroindenyl) SiMe2N(t—Bu)〕Ti(CH3)2) Preparation of
0.32 g of (N-tert-butylamino) (dimethyl) (1, 3-dimethyl-5, 6, 7, 8-tetrahydroindenyl) silane titanium dichloride (0.81 mmol) are suspended in 40 ml of diethyl ether. 0.56 ml of MeMgI (in ether, 3.0M) were added dropwise to the suspension with stirring over 20 minutes. After the addition was complete, the solution was stirred for 40 minutes. Thereafter, ether was removed under reduced pressure, the residue was extracted with pentane, the solution was filtered, and the filtrate was evaporated under reduced pressure to dryness, whereby 0.21 g (yield 73%) of the product was obtained. Polymerisation
The procedure of example 103 is followed except that 2 ml Isopar_E was mixed with 0.50. mu. mol of [ (1, 3-dimethyl-tetrahydroindenyl) SiMe2N(t—Bu)〕TiMe2And 0.50 micromoles of Lewis acid B (G)6F5)3To form a catalyst/cocatalyst mixture. The reaction mixture was 120 ℃. 797 grams of Isopar_E and 61 g of 1-octene were fed to the reactor, and hydrogen was added under a differential pressure of 20Psi (0.14 MPa differential). The ethylene pressure was 500Ssig (3.55 MPa). The polymerization time was 10 minutes. 29.2 g of an ethylene/octene copolymer were isolated. Its micro-melting index (I)2) Is 0.975.
Example 106
The procedure of example 105 is followed except that 2 ml Isopar_E was mixed with 0.10. mu. mol of [ (1, 3-dimethyl-tetrahydroindenyl) SiMe2N(t—Bu)〕TiMe2And 0.10 mmol of a Lewis acid, B (C)6F5)3To form a catalyst mixture. The reaction temperature was 90 ℃. 715 grams of Isopar were added to the reactor_E and 143 g of 1-octene are added and a hydrogen-ethylene pressure of 500Psig (3.45 MPa) at a differential pressure of 10psi (0.07 MPa differential pressure) is addedMegapascals). The polymerization time was 10 minutes. 64.5 g ofan ethylene/octene copolymer was isolated. Its melt index (12) was 0.346.
Example 107
The procedure of example 106 is followed except that 2 ml Isopar_E was mixed with 0.025. mu. mol of [ (C)5Me4)SiMe2N(t—bu)〕TiMe2And 0.025 micromoles of a Lewis acid, B (C)6F5)3To form a catalyst. The reaction temperature was 50 ℃. 679 g Ioopar was charged to the reactor_E and 179 g of 1-octene are added, and hydrogen is added under a differential pressure of 20psi (0.14 MPa). The ethylene pressure was 500Psig (3.55 MPa). The polymerization time was 60 minutes. 40.7 g of an ethylene/octene copolymer was isolated. The melt index (I2) was 0.66.
Example 108
The procedure was followed 107 except that Isopar was used at 2 ml_E was mixed with 2.00. mu. mol of [ (tetrahydrofluorenyl) -SiMe2N(t—Bu)〕Tibz2And 2.00. mu. moles of a Lewis acid, B (C)6F5)3Used to form a catalyst by reacting [ (N-tert-butylamino) (dimethyl) tetrahydrofluorenyl) silane]titanium dioxide with benzylmagnesium chloride. The reaction temperature was 150 ℃. 822 g of Isopar were added to the reactor_E and 36 g of 1-octene are added, and hydrogen is added at a differential pressure of 10psi (0.07 MPa). The ethylene pressure was 500Psig (3.55 MPa). The polymerization time was 15 minutes. 20.1 g of an ethylene/octene copolymer was isolated having a melt index (I2) of 0.327.
Example 109
The procedure of example 108 was followed except that the amount of the reaction solution was 2 mlIsopar_E was mixed with 2.00. mu. mol of [ (tetrahydrofluorenyl) -SiMe2N(t—Bu)〕Tibz2And 2.00. mu. moles of a Lewis acid, B (C)6F5)3To form a catalyst. The reaction temperature was 150 ℃. 822 g of Isopar were added to the reactor_E and 36 g of 1-octene were added and hydrogen was added at a differential pressure of 10Psi (0.07 MPa). Ethylene pressure 500Psig (3.55 MPa). The polymerization time was 15 minutes. 20.1 g of an ethylene/octene copolymer was isolated having a melt index (I2) of 0.327.
EXAMPLE 110 (N-tert-butylamino) dimethyl (η)5-tert-butylcyclopentadienyl) silane dimethyl titanium metal derivative polymeric tert-butylcyclopentadienyl lithium
To a 0 ℃ solution of 4.18 g (39.4 mmol), 6, 6-dimethylfulvene in 80 ml of diethyl ether was added 22.9 ml of a 1.72M (39.4 mmol) solution of methyllithium in diethyl ether. The resulting slurry was stirred for several days, then filtered, washed with pentane and dried in vacuo. (N-tert-butylamino) (dimethyl) (tert-butylcyclopentadienyl) silane
3.58 g (17.7 mmol) of tert-butylcyclopentadienyl lithium etherate are added to a solution of 3.35 g (20.2 mmol) of (N-tert-butylamino) (chloro) dimethylsilane in 75 ml of THF. The reaction mixture was stirred for several hours. And (4) removing the solvent. The residue was extracted with pentane and filtered. The pentane was removed in vacuo, whereby the product was obtained as a pale yellow oil. Yield was 2.87 g (64.6% yield). [ N-tert-butylamino) (dimethyl) (tert-butylcyclopentadienyl) silane]dilithium
15.8 mL of a 1.48M (23.4 mmol) solution of butyllithium in hexane was added to a solution of 2.87 g (11.4 mmol) of (N-t-butylamino) (dimethyl) (t-butylcyclopentadienyl) silane in 70 mL of diethyl ether, the resulting clear solution was stirred overnight, the solvent was removed under reduced pressure, and the yield was 107% [ N-t-butylamino) (dimethyl) (η -t-butylcyclopentadienyl) silane]as an impure product]pastel(t-butyl-C) dichloride5H3)SiMe2N(t—Bu)〕TiCl2)
0.60 g (2.27 mmol [ N-tert-butylamino) (dimethyl) (tert-butylcyclopentadienyl) silane]dilithium and 0.84 g (2.27 mmol) of TiCl as a solid are mixed in a beaker3(THF)3. To the mixture was added 40 ml of THF. The resulting dark purple solution was stirred for 10 minutes, then 0.35 g (1.25 mmol) of PbCl was added2. The reaction mixture was allowed to stir for less than one hour, the dark orange-brown reaction mixture was filtered off and the solvent was removed under reduced pressure. Using pentane as residueThe slurry was cooled in a freezer overnight and the yellow product was collected on a frit, washed with pentane and dried under reduced pressure yielding 0.58 g (69.6% yield) [ (N-tert-butylamino) (dimethyl) (η -tert-butylcyclopentadienyl) silane]dimethyl titanium ([ (tert-butyl-C)5H3)SiMe2N(t—Bu)〕Ti(CH3)2)
0.8 ml of 2.78M (2.22 mmol) CH3A solution of MgI in 15 ml of diethyl ether was slowly added over 20 minutes to 0.41 g (1.11)Millimole [ (N-tert-butylamino) (dimethyl) (η -tert-butylcyclopentadienyl) silane]titanium dichloride in 15 ml of diethyl ether solution was stirred for 20 minutes, then the solvent was removed, the residue was extracted with pentane, the resulting solution was filtered, and concentrated to an oil which was allowed to stand to crystallize in 0.34 g yield of 94.6%
Following the general polymerization procedure of example 109, in 2 mL Isopar_E was mixed with 0.25 mol of [ (tert-butyl-) (C5H3)SiMe2—N(t—Bu)〕TiMe2And 0.25 mmol of a Lewis acid, B (C)6F5)3To form a catalyst. The reaction temperature was 80 ℃. 1000 ml of Isopar were added_E, 100 grams of propylene and hydrogen at a differential pressure of 50psi (0.34 MPa). The ethylene pressure was 475Psig (3.38 MPa). The polymerization time was 10 minutes. 6.3 g of ethylene/propylene copolymer were isolated. The melt index (I2) was 1.291. The density was 0.8868 g/ml.
EXAMPLE 111 ethylene/norbornene copolymer
Following the general polymerization procedure of example 109, in 2 mL Isopar_E was mixed with 1.25. mu. mol [ (C)2Me4)SiMe2N(t—Bu)〕TiMe2And 1.87 micromoles of a Lewis acid, B (C)6F5)3To form the catalyst. The reaction temperature was 140 ℃.808 g of Isopar were added_E19.5 g of norbornene, and a differential pressure of 25Psig (0.17 MPa) of hydrogen. The ethylene pressure was 500psig (3.55 megapascals). The polymerization time was 10 minutes. 41.3 g of ethylene/norborneol are isolatedRandom copolymers of alkenes. It meltsMelt index (I2) of 0.587, using13C NMR spectrum showed that the polymer contained 2.38% by weight of norbornene.
EXAMPLE 112 ethylene/norbornene copolymer
Following the procedure of example 111, in 2 ml Isopar_E was mixed with 1.25. mu. mol of [ ((C))5Me4)SiMe2N(t—Bu)〕TiMe2And 1.87 micromoles of a Lewis acid, B (C)6F5)3To form the catalyst. The reaction temperature was 140 ℃. Adding 758 g Isopar_E39.0 g norbornene, and a differential pressure of 25psi (0.17 MPa) hydrogen. The ethylene pressure was 500Psig (3.55 MPa). The polymerization time was 10 minutes. 38.1 g of an ethylene/norbornene random copolymer was isolated. Its melt index (I2) was 1.52. By using13C NMR spectrum showed that the polymer contained 4.33% by weight of norbornene.
Example 113 ethylene/norbornene copolymer
Following the procedure of example 112, in 2 ml Isopar_E was mixed with 2.00. mu. mol of [ (C)5Me4)SiMe2N (t-Bu)]TimE and 3.00. mu. mol of a Lewis acid, B (C)6F5)3To produce a catalyst/cocatalyst mixture. The reaction temperature was 50 ℃. 1200 ml of Isopar containing 334.6 g of norbornene was added_E solution, and hydrogen at 5psig differential pressure (0.03 mpa). The ethylene pressure was 100psig (0.79 megapascals). The polymerization time was 30 minutes. 22.9 g of an ethylene/norbornene random copolymer were isolated. The melt index (I2) was 1.43. By using13C NMR spectrum of the polymer showed that the polymer contained 73.78% by weight of norbornene.The glass transition temperature Tg of the polymer was 83.8 ℃.
Example 114 polymerization of B (C) with Phenylbis (perfluorophenyl) borane Lewis acid6F5)2(C6H5) Preparation of
A250 ml portion was fired and evacuated, cooled to-78 deg.C, charged with 120 ml of mixed hexane solvent, and vacuum transferred into benzophenone carboxy sodium. The flask was backfilled with argon to 0.11 mpa pressure and bromopentafluorobenzene (10.00 g, 40.5 mmol, deoxygenated by purging with nitrogen) was added via syringe. Stirring of the mixture was started (with a magnetic stir bar) to give a clear, colorless solution. N-butyllithium (16.2 ml of a 2.5M hexane solution, 40.5 mmol) was added via syringe. With the addition of n-butyllithium, a clear, colorless solid was isolated from the mixture. This slurry was stirred at-78 ℃ for 70 minutes, then dichlorophenyl boron (3.22 g, 20.3 mmol, 0.50 eq) was added by syringe. After stirring at-78 ℃ for a further 30 minutes, no change was observed and the mixture was allowed to warm to ambient temperature. As the mixture was warmed, a cloudy white precipitate formed. Afterstirring for 15 minutes at 22 ℃, the flask was pulled under vacuum and the volume of the mixture was reduced to 50 ml. The mixture was filtered, the solid was extracted three times with 20 ml each time of mixed hexane solvent, and the filtrate was reduced to 20 ml under reduced pressure. The resulting solution was cooled to-78 ℃ to give a very thick slurry of colorless crystalline solid. The slurry was diluted by adding 20 ml of hexane. The solid was collected by filtration and dried under reduced pressure. Yield was 4.86 g, 57% yield. Polymerisation
The polymerization procedure of examples 3 to 37 was followed except that the reactor was chargedFill 850 ml Isopar_E, followed by the addition of 20 g of propylene. Hydrogen was then added at a differential pressure of 25psi (0.17 MPa) and the solution was heated to 130 deg.C. The solution was then saturated with 500psig (3.55 MPa) of ethylene. In 2 ml Isopar_E was mixed with 10. mu. mol of a metal complex [ (C)5Me4)SiMe2N(t—Bu)〕TiMe2And 10 micromoles of Lewis acid B (C)6F5)2(C6H5) The solution was transferred into the reactor to start the polymerization. The reaction was allowed to proceed for 15 minutes while supplying 500psig (3.55 mpa) of ethylene on demand. 2.8 g of an ethylene/propylene copolymer was obtained. The melt index (I2) was 7.52.
Example 115 ethylene/ethylidene norbornene copolymer
The procedure of example 111 was followed with two consecutive additions of catalyst solution in 2 ml Isopar_E by mixing 5.0. mu. mol [ (C)5Me4SiMe2N(t—Bu)〕TiMe2And 5.0 micromoles of Lewis acid, B (((R))6F5)3And (4) preparing. The reaction temperature was 130 ℃. 1200 ml of Isopar containing 50 ml of 5-ethylidene-2-norbornene are added_E solution, and hydrogen at a differential pressure of 50psi (0.34 mpa). The ethylene pressure was 475psig (3.38 megapascals). The polymerization time was 20 minutes. 59.9 g of an ethylene/5-ethylidene-2-norbornene copolymer were isolated. Its melt index (I2) was 1.55. By using13C NMR spectrum showed that the polymer contained 9.06% by weight of 5-ethylidene-2-norbornene.
Example 116
Various lewis acids used to prepare the catalysts of the present invention were tested for lewis acidity. Table V shows the acidity values and the methods used to determine these data.
TABLE 5 number of experiments Lewis acid acidity base
(kilocalorie/mole)
1 Phenylbis (perfluorophenyl) borane 0.01,2,3CH3-or NH3
2 Tris (2, 3, 5, 6-tetrafluorophenyl) -2.12CH3—
Borane complex
3-Tris (3, 4, 5-trifluorophenyl) methane-5.21″
Borane complexes
4 Tris (3, 4, 5, trifluorophenyl) aluminium-11.22″
5 Tris (1, 2, 2-trifluoroethylene) -12.31″
Borane complex
6 Tris (2, 3, 4, 5-tetrafluorophenyl) -15.22″
Borane complex
7 Tris (perfluorophenyl) borate-17.51″
8 Tris (perfluorophenyl) borane-17.81,5″
91, 3, 5-Cyclohexanetriol Borate-22.21NH3
101, 1, 1-Trimethylol ethane Borate-25.11″1HF/3-21 g process2AMl method3Acidity according to Childes' method, △ δ -0.77 ppm relative acidity-0.0 ppm4B(OC6F5)3 5Acidity according to Childes' method, △ δ is 1.10ppm, relative acidity is 0.33ppm
Claims (16)
1. A method of making a catalyst having a limited charge separation structure of the general formula:
LMX+XA-in the formula:
l is a derivative of a substituted delocalized π -bonded group conferring a constrained morphology on the metal active site, and containing up to 50 nonhydrogen atoms;
m is a metal of group 4 or the lanthanide series of the periodic Table of the elements;
x in each case independently is a hydride or a hydrocarbyl radical containing up to 20 carbon, silicon or germanium atoms, a silyl or germyl radical;
a-is a Lewis acid anion having a relative Lewis acidity greater than or equal to that of phenylbis (perfluorophenyl) borane, which anion is compatible with the metal cation,
the process steps include contacting a group 4 or lanthanide metal derivative of the general formula:
LMX2in the formula
L, M, and X are as defined above.
2. The process of claim 1 wherein M is titanium or zirconium.
m is titanium or zirconium;
cp is a cyclopentadienyl group or derivative thereof which is pi-bonded to M and is substituted by at least Z,
z is a divalent group containing oxygen, sulfur, boron or a member of group 14 of the periodic Table of the elements;
y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y may also together form a condensed ring system;
x is as defined in claim 1.
4. The process of claim 3 wherein-Z-T-is an aminosilyl or aminoalkanyl group.
5. The method of claim 4, wherein LMX2The molecular formula of (A) is:in the formula:
m is same as η5-cyclopentadienyl-bonded titanium or zirconium;
each occurrence of R 'is independently selected from the group consisting of hydrogen, silyl groups containing up to 20 carbon or silicon atoms, alkyl groups, aryl groups, and mixtures thereof, two or more R' groups on the cyclopentadienyl group optionally forming a fused ring system;
e is silicon or carbon;
x in each case independently is a hydride or an alkyl, aryl or halogen-substituted aryl group containing up to 20 carbon atoms;
m is 1 or 2.
6. The method of claim 5, wherein- (ER'2) m-NR' -contains up to 50 non-hydrogen atoms.
7. The method of claim 6, wherein- (ER'2) m-NR' -is (tert-butylamino)(dimethylsilyl) or (tert-butylamino) -1-eth-2-yl.
8. The method of claim 1, wherein X is a negative hydrogen ion or C1—C10A hydrocarbon group of (1).
9. The process of claim 8 wherein X is methyl or benzyl.
10. The process of claim 9, wherein R' in the cyclopentadienyl group is in each case hydrogen or C1—C5Alkyl, two or more of said R 'groups optionally together with the cyclopentadienyl group may form a tetrahydroindenyl or a tetrahydrofluorenyl group, R' on the nitrogen atom being a tert-butyl group
11. The process of any of the preceding claims wherein the lewis acid is a boron compound without a halogen group directly attached to the boron atom.
12. The method of claim 11 wherein the lewis acid is selected from the group consisting of: tris (pentafluorophenyl) borane, tris (2, 3, 5, 6-tetrafluorophenyl) borane, tris (2, 3, 4, 5-tetrafluorophenyl) borane, tris (3, 4, 5-trifluorophenyl) borane, tris (1, 2, 2-trifluoroethyl) borane, phenylbis (perfluorophenyl) borane, tris (3, 4, 5-trifluorophenyl) aluminum, tris (perfluorophenyl) borate, 1, 3, 5-cyclohexanetriol borate, and 1, 1, 1-trimethylolethane borate.
13. The process of claim 11 wherein the lewis acid is tris (pentafluorophenyl) borane.
14. The method of claim 11, wherein LMX2And A is selected from C5—C10Alkane or cycloalkane or their mixture in a solvent of 25-Contact at 50 ℃.
15. The method of claim 11, wherein LMX2And A are contacted in situ during the addition polymerization reaction.
16. The method of claim 11, wherein LMX2And A in an equivalent ratio of from 0.5: 1 to 1: 2.
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US5055438A (en) * | 1989-09-13 | 1991-10-08 | Exxon Chemical Patents, Inc. | Olefin polymerization catalysts |
US5026798A (en) * | 1989-09-13 | 1991-06-25 | Exxon Chemical Patents Inc. | Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system |
US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
CA2027145C (en) * | 1989-10-10 | 2002-12-10 | Michael J. Elder | Metallocene catalysts with lewis acids and aluminum alkyls |
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1992
- 1992-05-05 US US07/876,268 patent/US5721185A/en not_active Expired - Lifetime
- 1992-06-22 DE DE69206497T patent/DE69206497T2/en not_active Expired - Lifetime
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CA2072058C (en) | 2003-12-16 |
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CA2072058A1 (en) | 1992-12-25 |
EP0520732A1 (en) | 1992-12-30 |
DE69206497D1 (en) | 1996-01-18 |
JP3339883B2 (en) | 2002-10-28 |
MX9203162A (en) | 1993-02-01 |
KR100233966B1 (en) | 1999-12-15 |
US5721185A (en) | 1998-02-24 |
DE69206497T2 (en) | 1996-07-18 |
EP0520732B1 (en) | 1995-12-06 |
FI104085B (en) | 1999-11-15 |
FI104085B1 (en) | 1999-11-15 |
JPH05194641A (en) | 1993-08-03 |
CN1068125A (en) | 1993-01-20 |
FI922921A (en) | 1992-12-25 |
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